Method for combating harmful fungi

ABSTRACT

A method for control of harmful fungi is provided by treating the fungi, or the materials, plants, the soil or seeds to be protected against fungal infection, with an effective amount of a bisoxime of the formula I                    
     or a salt or adduct thereof, the index and the substituents having the following meanings: 
     R 1  is halogen, alkyl or haloalkyl; 
     R 2  is cyano, nitro, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, alkylamino, dialkylamino, alkylaminocarbonyl, substituted or unsubstituted phenyl, phenoxy or phenylthio; 
     n is 0, 1, 2 or 3; 
     R 3  is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl or phenylalkyl.

This application is a 371 of PCT/EP098/02880 filed May 5, 1998.

The present invention relates to a method of controlling harmful fungi,which comprises treating the fungi, or the materials, plants, the soilor seeds to be protected against fungal infection, with an effectiveamount of a bisoxime of the formula I

or a salt or adduct thereof, the index and the substituents having thefollowing meanings:

R¹ is halogen, C₁-C₆-alkyl or C₁-C₄-haloalkyl;

R² is cyano, nitro, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylamino,di-C₁-C₄-alkylamino, C₁-C₄-alkylaminocarbonyl,

phenyl, phenoxy or phenylthio, it being possible for these radicals tobe partially or fully halogenated in the phenyl moiety and/or to haveattached to them one to three of the following groups: cyano, formyl,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, phenyl or naphthyl;

n is 0, 1, 2 or 3, it being possible for the radicals R² to be differentif n is 2 or 3;

R³ is C₁-C₁₀-alkyl, C₁-C₆-haloalkyl, C_(3-C) ₆-alkenyl, C_(3-C)₆-haloalkenyl, C_(3-C) ₆-alkynyl, C_(3-C) ₆-haloalkynyl orphenyl-C₁-C₄-alkyl.

In addition, the invention relates to the use of the compounds I for thepreparation of a composition which is suitable for controlling harmfulfungi.

Bisoximes of the formula I defined at the outset have been disclosed inthe literature (cf. WO-A 95/18,789; WO-A 95/21,153; WO-A 95/21,154; WO-A95/21,156; WO-A 96/06,072; WO-A 96/16,026; WO-A 96/16,030; WO-A97/01,530; WO-A 97/02,255; DE Appl. No. 19 540 989; DE Appl. No. 19 545878; DE Appl. No. 19 548 370) as intermediates for the preparation offungicidally active ingredients of the type of the formula A:

However, apart from the usefulness of these compounds as intermediates,these documents do not suggest any additional possible applications ofthe bisoximes.

In addition, PCT/EP 96/01,306 describes processes for the preparation ofessentially isomerically pure bisoximes of the type of the compounds I.As regards the use of such compounds, this document refers to thesuitability as intermediate for the preparation of the compounds of type(A).

It is an object of the present invention to provide compounds withfungicidal properties.

We have found that this object is achieved by the prior-art bisoximes,which are suitable for controlling harmful fungi in an efficient manner.

The meaning of the collective terms used in the definition of thecompounds I can be seen, for example, from the relevant information inWO-A 95/21,156.

As regards their intended use for controlling harmful fungi,particularly suitable compounds I are those where R¹ is fluorine,chlorine or bromine (in particular chlorine) or methyl, ethyl, propyl oriso-propyl (in particular methyl or ethyl).

Other preferred compounds I are those where n is 1, 2 or 3 (especially 1or 2).

In the event that n is 1, preferred compounds I are those where theradical R² is bonded in the 4-position of the phenyl ring.

In the event that n is 2, preferred compounds I are those where theradicals R² are bonded in the relative position 2,4 or 3,4 (especially2,4).

In the event that n is 3, preferred compounds I are those where theradicals R² are bonded in the relative position 2,4,5 or 2,4,6(especially 2,4,5).

Especially suitable as radicals R² are halogen (in particular fluorine,chlorine and bromine), C₁-C₄-alkyl (in particular methyl),C₁-C₄-haloalkyl (in particular trifluoromethyl), C₁-C₄-alkoxy (inparticular methoxy), C₁-C₄-haloalkoxy (in particular trifluoromethoxy)and C₁-C₄-alkylthio (in particular methylthio), nitro and dimethylamino.

Additional preferred compounds I are those where R² (preferably one ofthe radicals R²) is phenyl, phenoxy or phenylthio (in particularphenyl), it being possible for these radicals to have attached to themin the phenyl moiety preferably one to three of the following groups:halogen (in particular chlorine and bromine), C₁-C₄-alkyl (in particularmethyl), C₁-C₄-haloalkyl (in particular trifluoromethyl), C₁-C₄-alkoxy(in particular methoxy), and C₁-C₄-haloalkoxy (in particulartrifluoromethoxy).

Other particularly preferred compounds I are those where at least one ofthe radicals R² is halogen.

With regard to the radical R³, preferred compounds I are those whichhave attached to them, in this position,

C₁-C₁₀-alkyl (especially C₁-C₄-alkyl),

C₃-C₆-alkenyl or C₃-C₆-haloalkenyl [especially C₃-C₄-alkenyl which mayhave attached to it one to three (in particular one or two) halogenatoms (in particular chlorine or bromine)],

C₃-C₆-alkynyl or C₃-C₆-haloalkynyl [especially C₃-C₄-alkynyl which mayhave attached to it one to three (in particular one or two) halogenatoms (in particular chlorine or bromine), or

phenyl-C₁-C₄-alkyl (in particular benzyl).

The compounds I are suitable as fungicides. They are distinguished byoutstanding activity against a broad spectrum of phytopathogenic fungi,in particular from the classes of the Ascomycetes, Deuteromycetes,Phycomycetes and Basidiomycetes. Some of them are systemically active,and they can be employed in crop protection as foliar- and soil-actingfungicides.

They are especially important for controlling a large number of fungi ona variety of crop plants, such as wheat, rye, barley, oats, rice, maize,grass, bananas, cotton, soya, coffee, sugarcane, grapevines, fruitspecies, ornamentals and vegetables such as cucumbers, beans, tomatoes,potatoes and cucurbits, and on the seeds of these plants.

Specifically, they are suitable for controlling the following plantdiseases:

Alternaria species on vegetables and fruit,

Botrytis cinerea (gray mold) on strawberries, vegetables, ornamentalsand grapevines,

Cercospora arachidicola on peanuts,

Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,

Erysiphe graminis (powdery mildew) on cereals,

Fusarium and Verticillium species on a variety of plants,

Helminthosporium species on cereals,

Mycosphaerella species on bananas,

Phytophthora infestans on potatoes and tomatoes,

Plasmopara viticola on grapevines,

Podosphaera leucotricha on apples,

Pseudocercosporella herpotrichoides on wheat and barley,

Pseudoperonospora species on hops and cucumbers,

Puccinia species on cereals,

Pyricularia oryzae on rice,

Rhizoctonia species on cotton, rice and turf,

Septoria nodorum on wheat,

Uncinula necator on grapevines,

Ustilago species on cereals and sugarcane, and

Venturia inaequalis (scab) on apples.

The compounds I are particularly suitable for controlling Erysiphespecies and Plasmopara viticola.

In addition, the compounds I are suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (eg. wood,paper, paint dispersions, fibers or fabrics) and in the protection ofstored products.

The compounds I are applied by treating the fungi, or the plants, seeds,materials or the soil to be protected against fungal infection, with afungicidally active amount of the active ingredients. Application may beeffected before or after infection of the materials, plants, or seeds bythe fungi.

When applied in crop protection, the rates of application are from 0.001to 5.0 kg, preferably 0.01 to 2 kg, in particular 0.05 to 1 kg, ofactive ingredient per ha, depending on the nature of the desired effect.

In the treatment of seed, amounts of from 0.001 to 0.1 g, preferably0.01 to 0.05 g, of active ingredient are generally required per kilogramof seed.

When used in the protection of materials or stored products, the rate ofapplication of active ingredient depends on the nature of the field ofapplication and of the desired effect. Normal rates of application inthe protection of materials are, for example, from 0.001 g to 2 kg,preferably 0.005 g to 1 kg, of active ingredient per cubic meter ofmaterial treated.

Due to the basic character of the nitrogen atoms, the compounds I mayform salts or adducts with acids and metal ions and may be applied inthe form of pure compounds and also in the form of salts or adducts ofthis kind.

Examples of inorganic acids are hydrohalic acids such as hydrogenfluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide,sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid andalkanoic acids such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids withstraight-chain or branched alkyl radicals having 1 to 20 carbon atoms),arylsulfonic acids or -disulfonic acids (aromatic radicals such asphenyl and naphthyl which have attached to them one or two sulfogroups), alkylphosphonic acids (phosphonic acids having straight-chainor branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonicacids or -diphosphonic acids (aromatic radicals such as phenyl andnaphthyl which have attached to them one or two phosphono radicals), itbeing possible for the alkyl or aryl radicals to have attached to themfurther substituents, eg. p-toluenesulfonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid andthe like.

Metal ions which are suitable are, in particular, the ions of theelements of the first to eighth sub-groups, particularly chromium,manganese, iron, cobalt, nickel, copper, zinc, and also of the secondmain group, particularly calcium and magnesium, and of the third andfourth main groups, in particular aluminum, tin and lead.

If appropriate, the metals may exist in the various valencies which theymay assume.

The compounds I or their salts can be converted into the customaryformulations, eg. solutions, emulsions, suspensions, dusts, powders,pastes and granules. The use form depends on the intended purpose; it isintended to ensure in each case a fine and uniform distribution of thecompound according to the invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it also being possible to use other organicsolvents as auxiliary solvents if water is used as the diluent.Auxiliaries which are suitable are essentially: solvents such asaromatics (eg. xylene), chlorinated aromatics (eg. chlorobenzenes),paraffins (eg. mineral oil fractions), alcohols (eg. methanol, butanol),ketones (eg. cyclohexanone), amines (eg. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(eg. kaolins, clays, talc, chalk) and ground synthetic minerals (eg.highly disperse silica, silicates); emulsifiers such as non-ionic andanionic emulsifiers (eg. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates) and dispersants such aslignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids andtheir alkali metal and alkaline earth metal salts, salts of sulfatedfatty alcohol glycol ether, condensates of sulfonated naphthalene andnaphthalene derivatives with formaldehyde, condensates of naphthalene orof naphthalenesulfonic acid with phenol or formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, eg. benzene, toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, chloroform, carbontetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone,strongly polar solvents, eg. dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Examples of solid carriers are mineral earths, such as silicagel, silicas, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, eg. ammonium sulfate, ammonium phosphate, ammonium nitrate,ureas, and products of vegetable origin, such as cereal meal, tree barkmeal, wood meal and nutshell meal, cellulose powders and other solidcarriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:

I. 5 parts by weight of a compound according to the invention are mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dust which comprises 5% by weight of the active ingredient.

II. 30 parts by weight of a compound according to the invention aremixed intimately with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which had been sprayedonto the surface of this silica gel. This gives a formulation of theactive ingredient with good adhesion properties (comprises 23% by weightof active ingredient).

III. 10 parts by weight of a compound according to the invention aredissolved in a mixture composed of 90 parts by weight of xylene, 6 partsby weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol ofoleic acid N-monoethanolamide, 2 parts by weight of calciumdodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 mol ofethylene oxide and 1 mol of castor oil (comprises 9% by weight of activeingredient).

IV. 20 parts by weight of a compound according to the invention aredissolved in-a mixture composed of 60 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil(comprises 16% by weight of active ingredient).

V. 80 parts by weight of a compound according to the invention are mixedthoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-alpha-sulfonate, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill (comprises 80% by weight of active ingredient).

VI. 90 parts by weight of a compound according to the invention aremixed with 10 parts by weight of N-methyl-α-pyrrolidone, which gives asolution which is suitable for use in the form of microdrops (comprises90% a by weight of active ingredient).

VII. 20 parts by weight of a compound according to the invention aredissolved in a mixture composed of 40 parts by weight of cyclohexanone,30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weightof the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.Pouring the solution into 100,000 parts by weight of water and finelydistributing it therein gives an aqueous dispersion which comprises0.02% by weight of the active ingredient.

VIII. 20 parts by weight of a compound according to the invention aremixed thoroughly with 3 parts by weight of sodiumdiisobutylnaphthalene-α-sulfonate, 17 parts by weight of the sodium saltof a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and the mixture is ground in a hammermill. Finely distributing the mixture in 20,000 parts by weight of watergives a spray mixture which comprises 0.1% by weight of the activeingredient.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, eg. in the form ofdirectly sprayable solutions, powders, suspensions or dispersions,emulsions, oil dispersions, pastes, dusts, materials for spreading, orgranules, by means of spraying, atomizing, dusting, spreading orpouring. The use forms depend entirely on the intended purposes; it isintended to ensure in each case the finest possible distribution of theactive ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances as such,or dissolved in an oil or solvent, can be homogenized in water by meansof wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within relatively wide ranges. In general, they are from 0.0001to 10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even to apply theactive ingredient without additives. Various types of oils, herbicides,fungicides, other pesticides, or bactericides may be added to the activeingredients, if appropriate just immediately prior to use (tank mix).These agents can be admixed with the agents according to the inventionin a weight ratio of 1:10 to 10:1.

In the use form as fungicides, the compositions according to theinvention can also be present together with other active ingredients,eg. with herbicides, insecticides, growth regulators, fungicides or elsewith fertilizers. Mixing the compounds I or the compositions comprisingthem in the use form as fungicides with other fungicides frequentlyresults in a broader fungicidal spectrum of action.

The following list of fungicides together with which the compoundsaccording to the invention can be used is intended to illustrate thepossible combinations, but not to impose any limitation:

sulfur, dithiocarbamates and their derivatives, such as iron(III)dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfides [sic], ammonia complex of zinc(N,N-ethylenebisdithiocarbamate), ammonia complex of zinc(N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

nitro derivatives, such as dinitro(1-methylheptyl)phenyl crotonate,2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitro-isophthalate;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(2-furyl)benzimidazole,2-(4-thiazolyl)benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide;

N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfodiamide,5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine-2-thiol1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide,N-formyl-N-morpholine-2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane;

amines such as 2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methylpropyl]piperidine,(8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine;

azoles such as1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl-ethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichloro-phenoxyethyl)-N′-imidazolyl-urea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,2,4′-difluoro-a-(1H-1,2,4-triazolyl-1-methyl)-benzhydryl alcohol,1-((bis-(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole,1-[2RS,4RS;2RS,4SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofuryl]-1H-1,2,4-triazole,2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,(+)-4-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)-1,3-dioxolan-2-yl]-phenyl4-chlorophenyl ether,(E)-(R,S)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)pent-1-en-3-ol,4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4,-triazolylmethyl)butyronitrile,3-(2,4-dichlorophenyl)-6-fluoro-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,(R,S)-2-(2,4-dichlorophenyl)-1-H-(1,2,4-triazol-1-yl)-hexano-2-ol,(1RS,5RS;1RS,5SR)-5-(4-chlorobenzyl)-2,2-dimethyl-l-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol,(R,S)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol,(+)-2-(2,4,-dichlorophenyl)-3-(1H-1,2,4-triazolyl)propyl1,1,2,2-tetrafluoroethyl ether,(E)-1-[1-[4-chloro-2-trifluoromethyl)-phenyl]imino)-2-propoxyethyl]-1H-imidazole,2-(4-chlorophenyl)-2-(1H -1,2,4-triazol-1-ylmethyl)hexanonitrile;

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene;

strobilurins such as methylE-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate,N-methyl-E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide,N-methyl-E-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide;

anilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-[4-methyl-6-cyclopropylpyrimidin-2-yl]aniline;

phenylpyrroles such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile;

cinnamamides such as3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholine;

and a variety of fungicides such as dodecylguanidine acetate,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,N-methyl-,N-ethyl-(4-trifluoromethyl,-2-[3′,4′-dimethoxyphenyl]benzamide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-[3,5-dichlorophenyl(-5-methyl-5-methoxymethyl]-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine.

SYNTHESIS EXAMPLES

With due modification of the starting compounds, the protocols shown inthe synthesis examples below were used for obtaining further compoundsI. The resulting compounds, together with physical data, are listed inthe tables which follow.

1. 1-[4-Chlorophenyl]propane-1,2-dione 2-oxime

First of all, 100 ml of saturated etheric hydrochloric acid were addeddropwise at −10° C. to −20° C. to a solution of 45 g (0.27 mol) of4-chloropropiophenone and 500 ml of toluene, and then a solution of 44.5g of n-butylnitrile in 200 ml of diethyl ether were added. After approx.24 hours at 20-220° C., the reaction mixture was poured into ice-water.The organic phase was isolated and washed three times with 1 N sodiumhydroxide solution and once with 3 N sodium hydroxide solution. Thesodium hydroxide phases were combined and acidified with 20% strengthsulfuric acid to a pH of 5. The precipitate formed during this processwas isolated and dissolved in tert-butyl methyl ether. The solution wasdried over sodium sulfate, and the solvent was removed under reducedpressure. This gave 81.4 g of the product as a pale yellow solid.

¹H NMR (CDCl₃, δ in ppm): 2.2 (s, 3H); 7.4 (m, 2H); 7.8 (m,2H); 9.0 (s,1H)

2. 4-Chlorophenyl-[E/E,Z/E]-2-hydroxyimino-1-methoxyiminopropane

68.5 g (0.82 mol) of O-methylhydroxylamine hydrochloride and 97 g (1.23mol) of pyridine were added to a mixture of 81.4 g of1-[4-chlorophenyl]-propane-1,2-dione 2-oxime and 500 ml of methanol.After approx. 24 hours at 22-25° C., the reaction mixture was pouredinto 10% strength hydrochloric acid. The mixture was extractedrepeatedly with tert-butyl methyl ether. The organic phases werecombined, washed with water and dried over sodium sulfate. The solventwas subsequently removed under reduced pressure. This gave 89.4 g of theproduct (isomer mixture).

4-Chlorophenyl-[E/E]-2-hydroxyimino-1-methoxyiminopropane

26.6 g (0.2 mol) of aluminum trichloride were slowly added at 40° C. toa solution of 89.4 g (0.39 mol) of4-chlorophenyl-[E/E,Z/E]-2-hydroxyimino-1-methoxyiminopropane in 500 mlof toluene. After 5 hours at 50° C. and a further 24 hours at 20-22° C.,the reaction mixture was poured into a mixture of ice and 10% strengthhydrochloric acid. The resulting mixture was extracted repeatedly withtert-butyl methyl ether. The organic phases were combined, washed with10% strength hydrochloric acid and subsequently with water, and dried.The solvent was subsequently removed under reduced pressure. This gave50.6 g of the product as a colorless solid (m.p.: 175-178° C.; isomericratio 98.5% E/E and 1.5% Z/E).

¹H NMR (CDCl₃, δ in ppm): 2.1 (s, 3H); 4.0 (s, 3H); 7.1 (m, 2H); 7.3 (m,2H); 8.0 (s, 1H)

TABLE I (I)

Physical data No. R¹ R² _(n) R³ */# [m.p. (° C.); IR (cm⁻¹); ¹H NMR (δin ppm)] I.1 CH₃ — CH₃ E/E m.p.: 160-162 I.2 CH₃ 3-CN CH₃ E/E m.p.:163-166 I.3 CH₃ 4-CN CH₃ E/E m.p.: 165-170 I.4 CH₃ 4-F CH₃ E/E m.p.:156-157 I.5 CH₃ 4-F CH₂CH₃ E/E m.p.: 75-91 I.6 CH₃ 4-F CH₂CH₃ E/Z m.p.:75-91 I.7 CH₃ 4-F CH(CH₃)₂ E/E m.p.: 120-130 I.8 CH₃ 4-F CH(CH₃)₂ E/E +E/Z m.p.: 77-80 I.9 CH₃ 4-F CH(CH₃)₂ E/Z m.p.: 74-77 I.10 CH₃ 4-FC(CH₃)₃ E/E m.p.: 96-130 I.11 CH₃ 4-F (CH₂)₃CH₃ E/E m.p.: 98-100 I.12CH₃ 4-F (CH₂)₃CH₃ E/Z IR: 1606, 1510, 1234, 1028 I.13 CH₃ 4-F (CH₂)₄CH₃E/Z IR: 1606, 1510, 1234, 1014 I.14 CH₃ 4-F (CH₂)₅CH₃ E/E m.p.: 66-74I.15 CH₃ 4-F CH₂—CH═CH₂ E/E + E/Z m.p.: 95-105 I.16 CH₃ 4-F CH₂C≡CH E/Em.p.: 149-150 I.17 CH₃ 4-F CH₂—C₆H₅ E/E + E/Z m.p.: 155-161 I.18 CH₃3-Cl CH₃ E/E m.p.: 151-152 I.19 CH₃ 4-Cl CH₃ E/E m.p.: 174-176 I.20 CH₃4-Cl CH₃ E/E + E/Z m.p.: 103-103 [sic] I.21 CH₃ 4-Cl CH₂CH₃ E/E m.p.:103-105 I.22 CH₃ 4-Cl CH₂CH₂CH₃ E/Z m.p.: 81-84 I.23 CH₃ 4-Cl CH(CH₃)₂E/E m.p.: 124-126 I.24 CH₃ 4-Cl (CH₂)₃CH₃ E/Z m.p.: 47-50 I.25 CH₃ 4-ClC(CH₃)₃ E/E m.p.: 132-135 I.26 CH₃ 4-Cl (CH₂)₅CH₃ E/E m.p.: 43-45 I.27CH₃ 4-Cl CH₂C≡CH E/E + E/Z m.p.: 108-111 I.28 CH₃ 4-Cl CH₂C≡CH E/E m.p.:149-154 I.29 CH₃ 4-Cl CH₂—C₆H₅ E/E m.p.: 113-116 I.30 CH₂CH₃ 4-Cl CH₃E/E m.p.: 159-161 I.31 CH₂CH₃ 4-Cl CH₂CH₂CH₃ E/Z IR: 1492, 1093, 992,940 I.32 CH₂CH₂ 4-Cl CH(CH₃)₂ E/E m.p.: 144 I.33 CH₂CH₂ 4-Cl (CH₂)₃CH₃E/E m.p.: 79-82 I.34 CH₂CH₃ 4-Cl (CH₂)₃CH₃ E/Z IR: 1492, 1093, 1014, 834I.35 CH₂CH₃ 4-Cl CH₂C≡CH E/E m.p.: 106-109 I.36 CH₃ 4-Br CH₃ E/E m.p.:175-178 I.37 CH₃ 4-Br CH₃ E/E + E/Z m.p.: 98-103 I.38 CH₃ 4-Br CH₂CH₃E/Z m.p.: 100-102 I.39 CH₃ 4-Br (CH₂)₃CH₂ E/E m.p.: 49-52 I.40 CH₃ 4-Br(CH₂)₅CH₂ E/Z m.p.: 50-53 I.41 CH₃ 4-Br CH₂C≡CH E/E m.p.: 119-120 I.42CH₃ 4-CH₃ CH₃ E/E m.p.: 152-155 I.43 CH₃ 4-CH(CH₃)₂ CH₃ E/E m.p.:182-183 I.44 CH₃ 4-CH(CH₃)₂ CH₂C≡CH E/E NMR: 2.1(s, 3H); 2.95(m, 1H);4.7(m, 2H) I.45 CH₃ 4-C(CH₃)₃ CH₃ E/Z m.p.: 183-188 I.46 CH₃ 4-C(CH₃)₃CH₃ E/E m.p.: 190-192 I.47 CH₃ 4-C(CH₃)₃ CH₃ E/E + E/Z m.p.: 78-81 I.48CH₃ 4-C(CH₃)₃ CH₂CH₃ E/E m.p.: 79-82 I.49 CH₃ 4-C(CH₃)₃ (CH₂)₃CH₃ E/EIR: 1634, 1017, 1001, 975 I.50 CH₃ 4-C(CH₃)₃ (CH₂)₅CH₃ E/Z IR: 1462,1364, 1017, 996 I.51 CH₃ 4-C(CH₃)₃ CH₂—C₆H₅ E/E + E/Z m.p.: 185-194 I.52CH₃ 4-C(CH₃)₃ CH₃ E/Z IR: 1462, 1263, 1057, 1034 I.53 CH₃ 2-CF₃ CH₂CH₃E/E m.p.: 116-118 I.54 CH₃ 3-CF₃ CH₃ E/E m.p.: 163-165 I.55 CH₃ 3-CF₃CH₃ E/Z IR: 1338, 1299, 1183, 1117 I.56 CH₃ 3-CF₃ CH₂CH₃ E/E m.p.:120-122 I.57 CH₃ 3-CF₃ CH₂CH₃ E/Z m.p.: 49-51 I.58 CH₃ 3-CF₃ (CH₂)₃CH₃E/E + E/Z IR: 1327, 1177, 1167, 1123 I.59 CH₃ 3-CF₃ CH₂—C₆H₅ E/E m.p.:117-120 I.60 CH₃ 3-CF₃ CH₂—C₆H₅ E/Z m.p.: 70-72 I.61 CH₃ 4-CF₃ CH₃ E/Em.p.: 198-201 I.62 CH₃ 4-CF₃ CH₃ E/Z + E/E IR: 1608, 1066, 1011, 998I.63 CH₃ 4-CF₃ CH₂CH₃ E/E m.p.: 171-174 I.64 CH₃ 4-CF₃ CH₂CH₃ E/Z m.p.:58-61 I.65 CH₃ 4-CF₃ (CH₂)₃CH₃ E/E m.p.: 118-124 I.66 CH₃ 4-CF₃(CH₂)₃CH₃ E/Z IR: 1326, 1168, 1139, 1070 I.67 CH₃ 4-CF₃ (CH₂)₅CH₃ E/Em.p.: 108-111 I.68 CH₃ 4-CF₃ (CH₂)₅CH₃ E/Z IR: 1325, 1168, 1129, 1070I.69 CH₃ 4-CF₃ CH₂—C₆H₅ E/E + E/Z m.p.: 150-153 I.70 CH₃ 4-CF₃ CH₂C≡CHE/E m.p.: 145-150 I.71 CH₃ 4-OCH₃ CH₃ E/Z m.p.: 93-95 I.72 CH₃ 4-OCH₃CH₂CH₃ E/Z m.p.: 71-74 I.73 CH₃ 4-OCH₃ (CH₂)₃CH₃ E/Z IR: 1517, 1252,1175, 1030 I.74 CH₃ 4-OCH₃ (CH₂)₅CH₃ E/E IR: 1512, 1251, 1175, 993 I.75CH₃ 4-OCH₃ CH₂—C₆H₅ E/Z m.p.: 94-96 I.76 CH₃ 2,4-Cl₂ CH₃ E/E m.p.:124-126 I.77 CH₃ 2,4-Cl₂ CH₂CH₃ E/E m.p.: 90-93 I.78 CH₃ 2,4-Cl₂(CH₂)₃CH₃ E/E m.p.: 62-66 I.79 CH₃ 2,4-Cl₂ (CH₂)₅CH₃ E/E m.p.: 80-84I.80 CH₃ 2,4-Cl₂ CH₂—C₆H₅ E/E m.p.: 136-139 I.81 CH₃ 2-F, 4-CF₃ CH₃ E/ENMR: 2.2(s, 3H); 4.0(s, 3H) I.82 CH₃ 2-F, 4-CF₃ CH₂CH₃ E/E IR: 1425,1330, 1133, 1048, 907 I.83 CH₃ 2-F, 4-CF₃ (CH₂)₃CH₃ E/Z + E/E IR: 1428,1331, 1176, 1133 I.84 CH₃ 2-F, 4-CF₃ (CH₂)₅CH₃ E/E IR: 1424, 1332, 1148,988 I.85 CH₃ 2-F, 4-CF₃ (CH₂)₅CH₃ E/Z + E/E IR: 1426, 1329, 1173, 1135I.86 CH₃ 2-F, 4-CF₃ CH₂—C₆H₅ E/E m.p.: 138 I.87 CH₃ 3-NO₂ CH₃ E/E m.p.:149-157 I.88 CH₃ 3-NO₂ CH₂CH₃ E/E m.p.: 147 I.89 CH₃ 4-N(CH₃)₂ CH₃ E/Zm.p.: 132-136 I.90 CH₃ 4-NH—COCH₂CH₃ CH₃ E/E m.p.: 210 I.91 CH₃4-NH—COCH₂CH₃ CH₃ E/Z m.p.: 190 I.92 CH₃ 4-NO₂ CH₃ E/E m.p.: 154-155I.93 CH₃ 4-C₆H₅ CH₃ E/E m.p.: 178-182 I.94 CH₃ 4-[4-F—C₆H₄] CH₃ E/Em.p.: 208-210 I.95 CH₃ 4-[4-Cl—C₆H₄] CH₃ E/E m.p.: 192-205 I.96 CH₃4-[4-CF₃—C₆H₄] CH₃ E/E m.p.: 205-208 I.97 CH₃ 4-[4-CHO—C₆H₄] CH₃ E/Em.p.: 165-175 I.98 CH₃ 4-[4-COCH₃—C₆H₄] CH₃ E/E m.p.: 145-150 I.99 CH₃4-[2-F, 4-CH₃—C₆H₃] CH₃ E/E m.p.: 170-176 I.100 CH₃ 4-[4-CH(CH₃)₂—C₆H₄]CH₃ E/E m.p.: 186-188 I.101 CH₃ 4-[3,5-(CF₃)₂—C₆H₃] CH₃ E/E m.p.:209-211 I.102 CH₃ 4-[3,5-Cl₂—C₆H₃] CH₃ E/E m.p.: 185-188 I.103 CH₃4-[2-OCH₃—C₆H₄] CH₃ E/E m.p.: 168 I.104 CH₃ 4-[4-CH₃—C₆H₄] CH₃ E/E m.p.:162-174 I.105 CH₃ 4-[2-naphthyl-C₆H₄] CH₃ E/E m.p.: 218-225

Examples of the action-against harmful fungi:

The fungicidal action of the compounds of the formula I was demonstratedby the following experiments:

The active ingredients were formulated as a 10% emulsion in a mixture of63% by weight of cyclohexanone and 27% by weight of emulsifier anddiluted with water to give the desired concentration.

1. Action against Erysiphe graminis var. tritiei (powdery mildew ofwheat)

Leaves of wheat seedlings (cultivar “Frühgold”) were first of alltreated with the aqueous formulation of the active ingredients (rate ofapplication: 250 ppm). After approx. 24 hours, the plants were dustedwith spores of powdery mildew wheat (Erysiphe graminis var. tritici).The plants thus treated were subsequently incubated for 7 days at 20-22°C. and a relative atmospheric humidity of 75-80%. The extent of fungaldevelopment was subsequently determined.

In this test, the plants which had been treated with the compounds I.5,I.15, I.19, I.20, I.21, I.22, I.27, I.28, I.36, I.42, I.63 and I.76showed a disease level of 10% or less, while the disease level of theuntreated (control) plants was 75%.

2. Action against Plasmopara viticola

Leaves of grapevines in pots, cultivar “Müller-Thurgau”, were sprayed torun-off point with an aqueous formulation of active ingredient. Toassess the long-term action of the substances, the plants were placed inthe greenhouse for 7 days after the spray coating had dried on. Onlythen were the leaves inoculated with an aqueous zoospore suspension ofPlasmopara viticola. Thereafter, the grapevines were placed first of allin a water-vapor-saturated chamber for 48 hours at 24° C. andsubsequently in the greenhouse for 5 days at from 20 to 30° C. Afterthis time, the plants were returned into a humid chamber for 16 hours toaccelerate the eruption of sporangiophores. The extent to which thedisease had developed on the undersides of the leaves was thendetermined visually.

In this test, the plants which had been treated with 250 ppm of thecompounds I.39, I.44 and I.83 showed a disease level of 15% or less,while the disease level of the untreated (control) plants was 70%.

We claim:
 1. A method of controlling harmful fungi, which comprisestreating the fungi, or the materials, plants, the soil or seeds to beprotected against fungal infection, with an effective amount of abisoxime of the formula I

or a salt or adduct thereof, wherein R¹ is halogen, C₁-C₆-alkyl orC₁-C₄-haloalkyl; R² is cyano, nitro, halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,C₁-C₄-alkylamino, di-C₁-C₄-alkylamino, C₁-C₄-alkylaminocarbonyl, phenyl,phenoxy or phenylthio, wherein the phenyl moiety is unsubstituted orpartially or fully halogenated, or the phenyl moiety carries one, two orthree substituents selected from the following groups: cyano, formyl,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, phenyl and naphthyl, in which case a non-substitutedcarbon ring member of the phenyl moiety carries a hydrogen atom or ahalogen atom; n is 0, 1, 2 or 3, and the radicals R² are identical ordifferent when n is 2 or 3; R³ is C₁-C₁₀-alkyl, C₁-C₆-haloalkyl,C₃-C₆-alkenyl, C₃-C₆-haloalkenyl, C₃-C₆-alkynyl, C₃-C₆-haloalkynyl orphenyl-C₁-C₄-alkyl.
 2. The method of claim 1, wherein R¹ is chloride,methyl, trifluoromethyl or ethyl.
 3. The method of claim 1, wherein n isdifferent from 0 and at least one of the radicals R² is halogen.
 4. Themethod of claim 1 wherein crop plants or their environment is treatedwith from 0.001 to 5.0 kg/ha of the bisoxime I.
 5. The method of claim 1wherein seeds, materials or areas are treated with from 0.01 to 20 g/m³of the bisoxime I.
 6. The method of claim 1, wherein n is 1 and R² isbonded in the 4-position of the phenyl ring, or n is 2 and the radicalsR² are bonded in the 2,4-position or the 3,4-position of the phenylring, or n is 3 and the radicals R² are bonded in the 2,4,5-position ofthe 2,4,6-position of the phenyl ring.
 7. The method of claim 6, whereinat least one of the radicals R² is halogen.
 8. The method of claim 1,wherein n is 1 and R² is bonded in the 4-position of the phenyl ring. 9.The method of claim 1, wherein n is 2 and the radicals R² are bonded inthe 2,4-position or the 3,4-position of the phenyl ring.
 10. The methodof claim 1, wherein n is 2 and the radicals R² are bonded in the2,4-position of the phenyl ring.
 11. The method of claim 1, wherein R²is selected from the group consisting of halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, nitroand dimethylamino.
 12. The method of claim 11, wherein n is 1 and R² isbonded in the 4-position of the phenyl ring, or n is 2 and the radicalsR² are bonded in the 2,4-position or the 3,4-position of the phenylring, or n is 3 and the radicals R² are bonded in the 2,4,5-position ofthe 2,4,6-position of the phenyl ring.
 13. The method of claim 12,wherein at least one of the radicals R² is halogen.
 14. The method ofclaim 1, wherein R² is selected from the group consisting of fluoride,chloride, bromide, methyl, trifluoromethyl, methoxy, trifluoromethoxy,methylthio, nitro and dimethylamino.
 15. The method of claim 1, whereinR³ is C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-haloalkenyl, C₃-C₆-alkynyl,C₃-C₆-haloalkynyl or phenyl-C₁-C₄-alkyl.
 16. The method of claim 1,wherein R³ is C₁-C₄-alkyl, C₃-C₄-alkenyl which is unsubstituted orcarries one, two or three halogen atoms, C₃-C₄-alkynyl which isunsubstituted or carries one, two or three halogen atoms, or is benzyl.